Cyanoacrylate compositions in non-flowable forms

ABSTRACT

The present invention relates to cyanoacrylate compositions in non-flowable and gel forms. More particularly, the present invention relates to non-flowable cyanoacrylate compositions which can be packaged in a convenient pocket-sized applicator dispenser for use in spreading the cyanoacrylate compositions onto substrates.

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to cyanoacrylate compositions innon-flowable forms. More particularly, the present invention relates tonon-flowable cyanoacrylate compositions which can be packaged in aconvenient pocket-sized applicator dispenser for use in spreading thecyanoacrylate compositions onto substrates.

Brief Description of Related Technology

Cyanoacrylate adhesive compositions, particularly α-cyanoacrylatecompositions, cure very rapidly and can be used on a variety ofsubstrates. Cyanoacrylate adhesive compositions are generally applied indrops of a low-viscosity liquid composition for adhesion at particularspot locations. The liquid compositions may include a thickener toprovide a composition capable of being retained to a substrate while thecomposition is being cured. Thickeners include acrylate resins, such aspolymethyl(meth)acrylate and polymethyl(meth)acrylate, polymericalkylcyanoacrylates, cellulose esters, such as cellulose acetate andcellulose butyrate, and polyvinyl ethers, such as polyvinylmethyl ether.See U.S. Pat. No. 3,742,018. In many applications, however, thedispensing and application of low-viscosity compositions is cumbersome.

Fumed silicas have in the past been added to cyanoacrylate compositionsto render the compositions thixotropic. See U.S. Pat. No. 4,533,422 andRe. 32,889, and U.S. Pat. No. 4,837,260. The thixotropic,fumed-silica-containing cyanoacrylate compositions are described asbeing in the form of a nonflowable gel which will not substantially movewhen placed on a substrate. These cyanoacrylate compositions may alsocontain thickeners, such as for the purpose of preventing the fumedsilica from settling in the composition. Disclosed thickeners includepoly(meth)acrylates, polycyanoacrylates, and poly(vinyl)acetates.

It is well known to formulate adhesives as “stick” compositions. Thepatent literature on stick adhesives is extensive and covers a broadrange of adhesive types, from emulsion adhesives through solvent basedadhesives, to contact adhesives as well as gelling and solidifyingadditives for the preparation of the sticks ranging from thermosettingthrough natural polymers to inert fillers. An example of one suchadhesive stick is sold under the trade name PrittStick™ by Henkel KGaA.This is an emulsion-based adhesive.

A number of patent documents identify adhesive compositions that havebeen formulated as soft-solids, and in some cases sticks. For instance,U.S. Pat. No. 5,433,775 discloses an adhesive stick consisting of awater based preparation of starch derivatives and a soap gel as theshaping gel-forming component. See also U.S. Pat. No. 5,371,131.

U.S. Pat. No. 3,846,363 relates to an adhesive crayon compositioncontaining a sorbitol-benzaldehyde reaction product as an additive. U.S.Pat. No. 4,639,475 discloses an adhesive stick composed of the reactionproduct of sorbitol and/or xylitol and benzaldehyde as the gel-formingcomposition together with an adhesive resin which is the reactionproduct of methyl vinyl ether/maleic acid anhydride copolymers withpartially neutralized acid phosphate esters of non-ionic wetting agentsof the lower alkylene oxide adduct type. Room temperature dimensionallystable cyanoacrylate compositions have also been prepared withcondensation products of aldehydes and ketones with polyols, such asdibenzylidene sorbital. See International Patent Application Nos. WO00/32709 and WO 01/91915, and Canadian Patent Application No. CA2353605.

Japanese unexamined patent application laid open (Kokai) 51-103939describes a stick-like epoxy adhesive and a stick-like epoxy hardeningagent which is used therewith. The sticks in JP '939 seem to be obtainedby suitably compounding a gelling agent and/or water and/or organicsolvent with a liquid or solution type epoxy adhesive and a epoxyhardening agent.

German Patent Document DE 199 57 677 A1 (Henkel KGaA) describes acyanoacrylate adhesive, coating or sealing material which also containsat least one condensation product of an aldehyde or ketone with apolyol. The adhesive may be in stick form.

Adhesive compositions have also been rendered non-flowable. For example,U.S. Pat. No. 4,497,916 discloses a continuous liquid phasenon-cyanoacrylate adhesive composition to which is added solid wax-likeparticles dispersed therein. These particles may be chosen frompolyethylene glycol materials having 4,000 to 20,000 molecular weight,stearic acid, acid waxes or stearic esters. The compositions disclosedin the '916 patent are formed by heating this combination of materialsin slurry form and applying it, while heated, to threads. Thecomposition then cools to obtain a non-mobile coating. This compositionrequires substantial preparation in order to obtain the composition andapply it on parts. U.S. Pat. No. 3,547,851 discloses anaerobiccompositions which have been rendered non-flowable through the inclusionof various waxes.

U.S. Pat. No. 6,451,927 describes a non-flowable poly(meth)acrylateadhesive composition having a polymeric matrix in sufficient quantitywhere it is non-flowable at temperatures up to 180° F. (82° C.) whilebeing dispensable at room temperature without the application of heat.

U.S. Pat. No. 6,797,107 describes an adhesive composition whichcomprises at least one cyanoacrylate monomer and at least onesolidifying polymer. The adhesive composition is reportedly capable ofpolymerizing to form an adhesive polymer and before such polymerizing,the adhesive composition is reported to have a liquifying point within aspecified temperature greater than about 20° C. and such polymerizing isreported to not substantially occur until the adhesive composition isliquefied. The adhesive composition is reported to be in solid form atroom temperature and the solidifying polymer is said to be a homopolymerof a certain structural formula, an example of which being caprolactone,such as Tone Polyol P-767-E and Tone Polymer P-767 Pellets.

Recently, Henkel Corporation introduced a line of adhesive products inthe form of a stick. For instance, LOCTITE QUICK STIK 248, 268, 668,548, 536 and PST 561 are members of that product line. However,conspicuously absent from this product line is one based oncyanoacrylates. One reason for this is that cyanoacrylates arenotoriously sensitive to premature polymerization or destabilization,which is because of the cure profile or physical characteristics of thecyanoacrylate.

And more recently, Loctite (R&D) Ltd. designed a cyanoacrylatecomposition set forth in U.S. Patent Application Publication No.2007/0092481, which speaks to a cyanoacrylate composition comprising a)at least one α-cyanoacrylate compound; and b) a polymer materialconstructed from poly(ethylene glycol) and polybutylene terephthalate)sections.

Accordingly, it would be desirable to provide a thickening agent for useas a constituent in cyanoacrylates that can be used in a variety ofconcentrations without adversely affecting the shelf life of thecyanoacrylate while having a dramatic impact on the viscosity,permitting the formulation of cyanoacrylates in a variety of viscositiesup to and including a non-flowable form, at room temperature.

Thus, there is a need for cyanoacrylate compositions in non-flowable andgel form, such as those that can be packaged in a convenientpocket-sized applicator dispenser for use in applying and spreading thecyanoacrylate compositions onto substrates.

SUMMARY OF THE INVENTION

In contrast to known cyanoacrylate adhesives, the present inventionprovides at least one cyanoacrylate compound in combination with apolymeric matrix present in an amount sufficient to render thecomposition non-flowable. The polymeric matrix may be selected frompolyhydroxyalkylacrylates, hydroxy-modified aliphatic hydrocarbons (suchas castor oil-based rheological additives), liquid polyester-basedrheological additives and combinations thereof.

In one desired embodiment of the present invention a cyanoacrylateadhesive composition is provided which includes aroom-temperature-flowable polymerizable cyanoacrylate monomer, apolymerization inhibitor, and a polymeric matrix material miscible orotherwise compatible with the monomer. The polymeric matrix andpolymerizable component readily form a stable mixture or combinationwithout phase separation of component parts.

In a further desirable embodiment the present invention provides anon-flowable adhesive composition, which includes a self-supportingcombination of a room-temperature-flowable polymerizable cyanoacrylatemonomer; a polymerization inhibitor; and a polymeric material misciblewith the cyanoacrylate, and present in an amount sufficient to renderthe composition non-flowable at temperatures of at least about 120° F.(49° C.), desirably about 160° F. (71° C.) and more desirably up toabout 180° F. (82° C.).

The present invention also contemplates a method of making thenon-flowable cyanoacrylate adhesive composition, as well as a method ofuse.

The present invention also contemplates an article of manufacture. Inthis embodiment there is included a dispensing container for housing anddispensing a non-flowable adhesive composition. The container includes agenerally elongate hollow body having first and second ends, with one ofthe ends having a dispense opening. The container houses an adhesivecomposition, which includes a room-temperature-flowable polymerizablecyanoacrylate monomer; a polymerization inhibitor; and a polymericmaterial miscible with the cyanoacrylate and the inhibitor and presentin an amount sufficient to render the composition non-flowable attemperatures of at least about 120° F. (49° C.), desirably about 160° F.(71° C.) and more desirably up to about 180° F. (82° C.).

In practical applications, these compositions are provided in anapplicator such that they can be conveniently dispensed to the desiredlocation. On their own, the cyanoacrylate adhesive compositions arenon-flowable at room temperature and at temperatures of at least about120° F. (49° C.), desirably about 160° F. (71° C.) and more desirably upto about 180° F. (82° C.); the compositions are however flowable uponexertion of a force and/or under elevated temperature conditions such asabove those noted above. For example, one convenient means of dispensingis a pocket-sized or hand-held lipstick-type container which can beeasily carried by the mechanic or maintenance worker for use as needed.Such a dispenser solves the problem of spillage in the environment whichcan be particularly problematic where contamination sensitive parts arepresent or when migration of adhesive is generally undesirable.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of a lipstick-type dispenser container witha cap.

FIG. 2 is a perspective view of a lipstick-type container showing theadhesive composition contained therein.

FIG. 3 is a perspective view of a dispenser container showing a notchedrim at the dispense opening.

FIG. 4 shows a dispense container having a concave section at itsdispense opening for receiving geometrically complimentary parts.

FIG. 5 shows a dispense container having both a concave section and anotched section at its dispense opening.

FIG. 6 is a perspective view of a dispensing container showing a moreexaggerated concave section at its dispensing opening.

FIG. 7 is a perspective view of a container and cap showing the dispenseopening defined by slotted apertures.

FIG. 8 shows a perspective view of a container and cap having thedispense opening defined by generally circular apertures.

FIG. 9 is a perspective view of a dispense container and cap showing thedispense opening having a concave surface portion and slotted aperturestherein.

FIG. 10 is a perspective view of a cap for a dispense container with oneend being concave.

FIG. 11 shows a top view of the cap of FIG. 10 showing elongateapertures for dispensing compositions.

FIG. 12 shows an exploded plan view of an alternative embodiments of alipstick-type dispenser container with a cap.

FIG. 13 shows a dispenser container, such as that of FIG. 1, partiallyin section, particularly identifying an interior collapsible linerwithin which is the non-flowable cyanoacrylate adhesive composition.

FIG. 14 is an exploded plan view of an alternative embodiment of alipstick-type dispenser container with a cap.

FIG. 15 is an exploded plan view of an alternative embodiment of alipstick-type dispenser container with a cap.

FIG. 16 is an exploded plan view of an alternative embodiment of alipstick-type dispenser container with a cap.

FIG. 17 is an exploded plan view of an alternative embodiment of alipstick-type dispenser container with a cap.

FIG. 18 is a sectional view of an alternative embodiment of a dispensercontainer with a cap identifying an interior cavity within which is thenon-flowable cyanoacrylate adhesive composition.

FIG. 19 is a sectional view of the dispenser container of FIG. 18 withthe dispenser actuator in a dispensing position.

FIG. 20 is a sectional view of the dispenser container of FIG. 18 withthe dispenser actuator in a fill position.

FIG. 21 is a sectional view of an alternative embodiment of a dispensercontainer with a cap identifying an interior cavity within which is twodifferent non-flowable cyanoacrylate adhesive compositions to be mixedand dispensed as one composition.

FIG. 22 is a sectional view of the dispenser container of FIG. 21 withthe dispenser actuator in a mixing position.

FIG. 23 is a sectional view of the dispenser container of FIG. 21 withthe dispenser actuator in a dispensing position.

FIG. 24 is a sectional view of the dispenser container of FIG. 21 withthe dispenser actuator in a fill position.

FIG. 25 is a sectional view of an alternative embodiment of a dispensercontainer with a cap identifying an interior cavity within which is twodifferent non-flowable cyanoacrylate adhesive compositions to bedispensed as two compositions.

FIG. 26 is a sectional view of the dispenser container of FIG. 25 withthe dispenser actuator in a first fill position.

FIG. 27 is a sectional view of the dispenser container of FIG. 25 withthe dispenser actuator in a second fill position.

FIG. 28 is a sectional view of the dispenser container of FIG. 25 withthe dispenser actuator in a dispensing position.

FIG. 29 is a bottom view of the dispenser actuator of FIG. 25.

FIG. 30 is a bottom view of an alternative dispenser actuator fordispensing the compositions as one.

DETAILED DESCRIPTION OF THE INVENTION

The compositions and articles of manufacture of the present inventioninclude at least one α-cyanoacrylate

The cyanoacrylate compositions of this invention as described abovecontain an α-cyanoacrylate monomer of the formula:

where R¹ represents a straight chain or branched chain alkyl grouphaving 1 to 12 carbon atoms (which may be substituted with a substituentsuch as a halogen atom or an alkoxy group), a straight chain or branchedchain alkenyl group having 2 to 12 carbon atoms, a straight chain orbranched chain alkynyl group having 2 to 12 carbon atoms, a cycloalkylgroup, an aralkyl group or any aryl group. Specific examples of R¹ are amethyl group, an ethyl group, an n-propyl group, an isopropyl group, ann-butyl group, an isobutyl group, a pentyl group, a hexyl group, anallyl group, a methallyl group, a crotyl group, a propargyl group, acyclohexyl group, a benzyl group, a phenyl group, a cresyl group, a2-choroethyl group, a 3-choropropyl group, a 2-chorobutyl group, atrifluoroethyl group, a 2-methoxyethyl group, a 3-methoxybutyl group anda 2-ethoxyethyl group. Ethyl cyanoacrylate is the preferred monomer foruse in the inventive compositions.

A single α-cyanoacrylate monomer or a mixture of two or more of theseα-cyanoacrylate monomers can be used. Generally, the aboveα-cyanoacrylate monomer used alone as an adhesive, and one or morecomponents such as those set forth below, are used to formulate acommercial composition. The additional components includes, but are notlimited to, accelerators; anionic polymerization inhibitors; radicalpolymerization inhibitors; thickeners; additives, such as plasticizers,heat stabilizers and toughening agents; and/or perfumes, dyes, andpigments.

A suitable amount of α-cyanoacrylate monomer present in the adhesivecomposition is about 50 to 99.5% by weight, preferably 60 to 90% byweight, based on the total weight of the adhesive composition.

An anionic polymerization inhibitor is generally added to theα-cyanoacrylate type adhesive composition, e.g., in an amount of about0.0001 to 10% by weight based on the total weight of the adhesivecomposition, to increase the stability of the adhesive compositionduring storage. Non-limiting examples of useful inhibitors includesulfur dioxide, sulfur trioxide, nitric oxide, hydrogen fluoride,organic sultone inhibitors, boron trifluoride and methane sulfonic acid,aromatic sulfonic acids, aliphatic sulfonic acids, and sulfones. Theamount of inhibitor will, suitably be any convenient amount in order toslow down cure of the composition. Desirably, inhibitors of anionicpolymerization are present at about 0.0001% to about 0.1% by weight ofthe adhesive composition.

Suitable examples of radical polymerization inhibitors include, forexample, hydroquinone and hydroquinone monomethyl ether. A radicalpolymerization inhibitor is added, e.g., in an amount of about 0.001 to2.0% by weight, particularly 0.03 to 0.5% by weight, based on the totalweight of the adhesive composition, for the purpose of capturingradicals which are formed by light during storage.

The present invention includes the presence of the polymeric matrix inamounts of about 2.5% to about 20%, for instance about 5% to about 15%,such as about 7% to about 10%, by weight of the total composition. Whenpresent in these amounts, the non-flowability characteristics of acomposition can be obtained with minimal undesirable effects, such asloss of substantial tensile properties. Additionally, these materialscan be added directly in solid form, such as in powder or particulateform, without pre-melting of the particles or even heating of thepolymerizable materials. It is often practical, however, to slightlyheat the polymerizable materials before or after incorporating thepolymeric matrix for the sake of expediency. This is not necessary toobtain the non-flowable characteristics but is used as a practical andexpedient processing measure.

Specific polymeric materials useful herein as the polymeric matrixinclude hydroxyl modified aliphatic hydrocarbons and liquidpolyester-based rheological additives. Hydroxy modified aliphatichydrocarbons include THIXCIN E, THIXCIN R, THIXCIN GR, THIXATROL ST andTHIXATROL GST available from Rheox Inc., Hightstown, N.J. These modifiedaliphatic hydrocarbons are castor oil based materials. The hydroxylmodified aliphatic hydrocarbons are partially dehydrated castor oil orpartially dehydrated glycerides of 12-hydrostearic acid.

The polymeric matrix includes an organic material which generally has amelting point or softening point range in the range of about 200° F.(93° C.) to about 500° F. (260° C.), more desirably greater than 250° F.(121° C.) to about 500° F. (260° C.). Polymeric materials useful in thepresent invention may be selected from hydroxy modified aliphatichydrocarbons (such as castor oil-based rheological additives), andcombinations thereof.

In addition, the polymeric matrix may further includepolyhydroxyalkylaciylates.

The cyanoacrylate composition in non-flowable form may also be presentin a multi-part arrangement, such as a two part arrangement. See e.g.FIGS. 25-30.

In such case, the cyanoacrylate component should be placed in onechamber and an accelerator should be placed in another chamber of thecontainer. The polymeric matrix for the cyanoacrylate component shouldbe selected from one of the materials identified above. The polymericmatrix for the accelerator may be the same or different and may beselected from one or more of the recited materials above. Or, thepolymeric matrix may be selected from urea-urethanes, amine modifiedaliphatic hydrocarbons, polyamides, polyacrylamides, polyimides, orliquid polyester-amide based rheological additives. Of particularutility are polyamide materials having a melting point of about 260° F.(127° C.). One such polyamide is commercially available as anon-reactive free flowing powder under the tradename DISPARLON 6200,from King Industries Specialties Company, Norwalk, Conn. Otherpolyamides include DISPARLON 6100 and 6500. The recommended use inaccordance with commercially available data sheets for DISPARLON 6200 isfor epoxy adhesive and potting compounds in amounts of about 0.5% toabout 3% by weight; the recommended use in accordance with commerciallyavailable data sheets for DISPARLON 6500 is for epoxy adhesive andpotting compounds in amounts of about 0.5% to about 3% by weight.

The polyamide materials desirably have a particle size less than about15 microns, although other particle sizes are useful. As previouslymentioned, the melting or softening point of the polymeric matrixmaterials ranges from about 200° F. (93° C.) to about 500° F. (260° C.).In a particularly desirable embodiment, a polyamide having a meltingpoint of about 250° F.-270° F. (121° C.-132° C.) and desirably about260° F. (127° C.) is employed.

A more particular description of a urea-urethane includes a combinationof an alkali metal cation and the reaction product of (a) apolyfunctional isocyanate and an hydroxy and an amine; or (b) a phosgeneor phosgene derivative, and a compound having 3 to 7 polyethylene etherunits terminated at one end with an ether group and at the other endwith a reactive functional group selected from an amine, an amide, athiol or an alcohol; or (c) a monohydroxy compound, a diisocyanate and apolyamine. When the reaction product described in (c) is employed it isgenerally formed by first reacting a monohydroxy compound with adiisocyanate to form a mono-isocyanate adduct, and subsequently reactingthe mono-isocyanate reaction product with a polyamine in the presence ofan alkali metal salt and aprotic solvent, as described in U.S. Pat. No.4,314,924, the disclosure of which is hereby expressly incorporatedherein by reference. A commercially available version of the reactionproduct described in (c) is believed to be BYK-410, from BYK-Chemie,Wallingford, Conn. BYK-Chemie describes this reaction product as aurea-urethane.

Useful isocyanates for forming the reaction product(s) of the additiveinclude polyisocyanates such as phenyl diisocyanate, toluenediisocyanate, 4,4′-diphenyl diisocyanate, 4,4′-diphenylene methanediisocyanate, dianisidine diisocyanate, 1,5-naphthalene diisocyanate,4,4′-diphenyl ether diisocyanate, p-phenylene diisocyanate,4,4′-dicyclo-hexylmethane diisocyanate, 1,3-bis-(isocyanatomethyl)cyclohexane, cyclohexylene diisocyanate, tetrachlorophenylenediisocyanate, 2,6-diethyl-p-phenylenediisocyanate, and3,5-diethyl-4,4′-diisocyanatodiphenylmethane. Still otherpolyisocyanates that may be used are polyisocyanates obtained byreacting polyamines containing terminal, primary and secondary aminegroups or polyhydric alcohols, for example, the alkane, cycloalkane,alkene and cycloalkane polyols such as glycerol, ethylene glycol,bisphenol-A, 4,4′-dihydroxy-phenyldimethylmethane-substitutedbisphenol-A, and the like, with an excess of any of the above-describedisocyanates.

Useful alcohols for reacting with the polyisocyanates also includepolyethyl glycol ethers having 3-7 ethylene oxide repeating units andone end terminated with an ether or an ester, polyether alcohols,polyester alcohols, as well as alcohols based on polybutadiene. Thespecific type of alcohol chosen and the molecular weight range can bevaried to achieve the desired effect. Generally, monohydroxy compounds,straight or branched chain aliphatic or cyclic primary or secondaryalcohols containing C₅₋₂₅, and alkoxylated derivatives of thesemonohydroxy compounds are useful.

Phosgene and phosgene derivatives, such as bischloroformates, may beused to make the reaction product of the additive (c). These compoundsare reacted with a nitrogen-containing compound, such as an amine, anamide or a thiol to form the adduct. Phosgenes and phosgene derivativesmay also be reacted with an alcohol to form, the reaction product.

The alkali metal cations are usually provided in the form of a halidesalt. For example, sodium, potassium and lithium halide salts areuseful. In particular, sodium chloride, sodium iodide, sodium bromide,potassium chloride, potassium iodide, potassium bromide, lithiumchloride, lithium iodide, lithium bromide and combinations thereof maybe employed.

The reaction products of additive (c) of the present invention areusually present in and added to the composition with an alkali metalsalt, in a solvent carrier. The solvents are desirably polar aproticsolvents in which the reaction to form the reaction product was carriedout. For example, N-methyl pyrrolidone, dimethylsulfoxide,hexamethylphosphoric acid triamide, N,N-dimethylformamide,N,N,N′,N′-tetramethylurea, N,N-dimethylacetamide, N-butylpyrrolidone,tetrahydrofuran and diethylether may be employed.

One particularly desirable additive is the combination of a lithium saltand a reaction product which is formed by reacting a monohydroxycompound with a diisocyanate compound to form a mono-isocyanate firstadduct, which is subsequently reacted with a polyamine in the presenceof lithium chloride and 1-methy-2-pyrrolidone to form a second adduct. Acommercially available additive of this sort is sold by BYK Chemie,Wallingford, Conn. under the tradename BYK 410. This commerciallyavailable additive is described by BYK-Chemie product literature asbeing a urea urethane having a minor amount of lithium chloride presentin a 1-methyl-2 pyrrolidone solvent.

Amines which can be reacted with phosgene or phosgene derivatives tomake the reaction product include those which conform to the generalformula R¹¹—NH₂, where R¹¹ is aliphatic or aromatic. Desirable aliphaticamines include polyethylene glycol ether amines. Desirable aromaticamines include those having polyethylene glycol ether substitution onthe aromatic ring.

For example, commercially available amines sold under the tradenameJEFFAMINE by Huntsman Corporation, Houston, may be employed. Examplesinclude JEFFAMINE D-230, JEFFAMINE D-400, JEFFAMINE D-2000, JEFFAMINET-403, JEFFAMINE ED-600, JEFFAMINE ED-900, JEFFAMINE ED-2001, JEFFAMINEEDR-148, JEFFAMINE XTJ-509, JEFFAMINE T-3000, JEFFAMINE T-5000, andcombinations thereof.

The JEFFAMINE D series are diamine based products and may be representedby:

-   -   (CAS Registry No. 904610-0)        where x is about 2.6 (for JEFFAMINE D-230), 5.6 (for JEFFAMINE        D-400) and 33.1 (for JEFFAMINE D-2000), respectively.

The JEFFAMINE T series are trifunctional amine products based onpropylene oxide and may be represented by:

where x, y and z are set forth below in Table A.

TABLE A JEFFAMINE Approx. Product Initiator (A) Mol. Wt. Mole % T-403Trimethylolpropane 440 5-6 T-3000 Glycerine 3,000 50 T-5000 Glycerine5,000 85

More specifically, the JEFFAMINE T-403 product is a trifunctional amineand may be represented by:

where x+y+z is 5.3. (CAS Registry No. 39423-51-3)

The JEFFAMINE ED series are polyether diamine-based products and may berepresented by:

where a, b and c are set forth below in Table B.

TABLE B JEFFAMINE Approx. Value Approx. Product B a + c Mol. Wt. ED-6008.5 2.5 600 ED-900 15.5 2.5 900 ED-2001 40.5 2.5 2,000

Amides useful for reacting with the phosgene or phosgene derivativesinclude those which correspond to the following formula:

where R¹² may be an aliphatic or aromatic, substituted or unsubstituted,hydrocarbon or heterohydrocarbon, substituted or unsubstituted, havingC₁₋₃₆.

Alcohols useful in forming the reaction product with the phosgene orphosgene derivatives include those described above.

Another polymeric matrix useful herein includes hydroxyl or aminemodified aliphatic hydrocarbons and liquid polyester-amide basedrheological additives. Hydroxy or amine modified aliphatic hydrocarbonsinclude THIXCIN R, THIXCIN GR, THIXATROL ST and THIXATROL GST availablefrom Rheox Inc., Hightstown, N.J. These modified aliphatic hydrocarbonsare castor oil based materials. The hydroxyl modified aliphatichydrocarbons are partially dehydrated castor oil or partially dehydratedglycerides of 12-hydrostearic acid. These hydrocarbons may be furthermodified with polyamides to form polyamides of hydroxyl stearic acid aredescribed as being useful polyamides.

Liquid polyester-amide based rheological additives include THIXATROLTSR, THIXATROL SR and THIXATROL VF rheological additives available fromRheox Inc., Hightstown, N.J. These rheological additives are describedto be reaction products polycarboxylic acids, polyamines, alkoxylatedpolyols and capping agents. Useful polycaboxylic acids include sebacicacid, poly(butadiene) dioic acids, dodecane dicarboxylic acid and thelike. Suitable polyamines include diamine alkyls. Capping agents aredescribed as being monocarboxylic acids having aliphatic unsaturation.

Thickeners, plasticizers, pigments, dyes, diluents, fillers, and otheragents common to the art can be employed in any reasonable manner toproduce desired functional characteristics, providing they do notsignificantly interfere with the monomer polymerization. TEFLON(polytetrafluoroethylene) and polyethylene are non-limiting examples.

As noted a thickener may be added to increase the viscosity of theα-cyanoacrylate adhesive composition; however, with the recitedpolymeric material, it may not be as desirable. Nevertheless, variouspolymers can be used as thickeners, and examples include poly(methylmethacrylate), methacrylate-type copolymers, acrylic rubbers, cellulosederivatives, polyvinyl acetate and poly(α-cyanoacrylate). A suitableamount of thickener is generally about 0.01 to 30% by weight, preferably5 to 25% by weight based on the total weight of the cyanoacrylateadhesive composition.

Likewise, fumed silicas, hydrophobic silicas and certain fumed silicafillers treated with polydialkylsiloxanes or trialkylsilanes asdescribed in U.S. Pat. No. 4,533,422 (Litke) may also be usefullyemployed in cyanoacrylate compositions as thickeners or thixotropes,e.g., in an amount of 0.01 to 20.0% by weight, preferably 5.0 to 20.0%by weight, based on the total weight of the cyanoacrylate adhesivecomposition. Again, however, with the recited polymeric materialpresent, it may not be as desirable.

Perfumes, dyes, pigments, etc., may be added depending on use purposesin amounts which do not adversely affect the stability of theα-cyanoacrylate monomer. The use of such additives is within the skillof those practicing in the cyanoacrylate adhesive art and need not bedetailed herein.

A cyanoacrylate accelerator may be used in a conventional manner such asin an amount of about 0.01 to 5.0% by weight, preferably 0.01 to 2.0% byweight, based on the total weight of the composition. Non-limitingexamples of useful accelerators include calixarenes, oxacalixarenes,phthalic anhydride, non-ionic surface active agents, silacrowns, crownethers and cyclodextrins, poly)ethyleneglycol) di(meth)acrylates andethoxylated hydric compounds. See e.g. U.S. Pat. Nos. 4,170,585;4,450,265; 6,294,629; and 6,475,331, the contents of which are allincorporated herein by reference.

Preparation of the compositions and products of the present inventioncan be achieved by simple admixture of the polymeric material into thepolymerizable composition. Desirably, these constituents are mixed atabout 1000 rpm under slightly elevated temperature conditions, forexample, 80° C. to 100° C. The polymeric material may then be added,while maintaining the temperature at about 80° C. to 100° C. The actualtemperature used may vary depending upon the melting point of the matrixmaterial. After the polymeric material has been added, metallic powderand/or graphite may be added with the mixing speed increased to about1500 rpm. The so-formed composition is dispensed into lipstick-typedispensers while hot. The dispensers are then allowed to cool to createthe composition of the present invention. The polymeric material may bepreheated to the above-described temperatures before its addition.

Mixing is performed for a time sufficient to incorporate the polymericmaterial, into the polymerizable composition, which can vary dependingon the batch size. Generally, only seconds or minutes are required toachieve the desired blending in of the polymeric material. Thecomposition will render itself non-flowable in approximately 2 to about100 hours at room temperature depending on the nature of thepolymerizable composition. This is due to the unique nature of thepolymeric material, which is designed to be swellable and effectivelyform a branched matrix in situ. While not wishing to be bound by anyparticular hypothesis, it is believed that the particles of polymericmaterial retain their particulate nature, yet imbibe large amounts ofthe polymerizable composition. In doing so, they lend the non-flowablecharacteristics to the polymerizable composition, yet apply smoothly toa surface by virtue of its particulate nature. It appears that a portionof the matrix particle is solubilized which permits the imbibing, and aportion remains unsolubilized which allows for retention of itsparticulate form. After the polymeric material has been added, theso-formed composition may be dispensed into lipstick-type dispenserswhile hot. The dispensers are then allowed to cool to create thecomposition and article of manufacture of the present invention.

The present invention also contemplates an article of manufacture whichincludes the above-mentioned non-flowable cyanoacrylate adhesivecomposition in a dispenser container, with or without an opticalapplicator. Desirably, the dispenser is of a pocket-sized dimension suchthat it easily can be carried by the mechanic or maintenance worker in apocket, apron or tool box without fear of spillage or contamination ofsensitive parts and use it as needed.

The container is generally fitted with a cap which fits over and aroundthe container walls.

At the container end opposite the dispense opening, i.e., the bottom endof the container is proximally located a mechanism for mechanicallyadvancing the adhesive. These mechanisms are generally well known in theart and include a pusher means which can include a knob located at thebottom of the container which when turned in one direction advances theadhesive contained therein to the dispense opening and when turned inthe other direction moves the cyanoacrylate adhesive in the oppositedirection. This mechanism for mechanically advancing the cyanoacrylateadhesive composition creates a friction on the non-flowablecyanoacrylate adhesive compositions, which friction renders thecomposition free flowable while it is applied.

More specifically, reference to FIGS. 1-30 depicts an article ofmanufacture in more particular detail. FIG. 1 shows dispense container10 having a generally elongated tubular shape defined by wall 20 andhaving a dispense end defined by perimeter 21. Cap 50 as shown isdesigned for closingly engaging tubular wall 20 by fitting thereover.Composition 30 is shown in FIG. 1 within container 10. FIG. 2 showscomposition 30 being advanced above perimeter 21 using knurled knob 40whish was turned to advance the composition. Turning knob 40 in theopposite direction caused composition 30 to descend back within thecontainer.

FIG. 1 shows container 10 having a generally elongate tubular shapedefined by wall 20 and having a dispense end defined by perimeter 21.Cap 50 as shown is designed for closingly engaging tubular wall 20 byfitting thereover. Desirably, cap 50 engages the tubular wall 20 toprovide a barrier against ambient humidity to prevent premature curingof the cyanoacrylate adhesive composition disposed within container 10.Metal tubular walls (not shown in FIG. 1, but shown as 23 in FIG. 4) ora metal sleeve, for example aluminum, within which the cyanoacrylateadhesive composition may be disposed and optionally metal caps, areuseful. This metal sleeve further protects against prematurepolymerization. Composition 30 is shown in FIG. 1 within container 10.FIG. 2 shows composition 30 being advanced above perimeter 21 usingknurled knob 40 which was turned to mechanically advance the compositionwithin container 10. In one embodiment, knob 40 may be turned in theopposition direction to cause composition 30 to descend back withincontainer 10.

FIG. 3 shows container 10 as having a dispense end perimeter 22, whichdefines the opening, and has an alternative notched shape. Such a designcould alternatively be sinusoidal or have other geometric shapes whichcan be tailored to the type of surface on which the composition is to beapplied. For example, FIG. 4 shows container 10 having opposed concavesurfaces in its perimeter 23 for accommodating parts having roundedsurfaces such as a bolt, screw or rod-like parts. FIG. 5 shows aperimeter 24 with opposed concave surfaces in combination with notchedsections.

FIG. 6 shows a container 10 having more exaggerated opposed concavesections at its perimeter 25.

FIG. 7 shows a container 10 having a dispense end with end surface 65and elongated apertures 70 through which the composition is dispensed.

FIG. 8 shows a different aperture shape in the form of generallycircular apertures 71.

FIG. 9 shows container 10 having an end surface 66 in which apertures 72are both elongated and concave since they follow the geometry of the endsurface 66. Cap 51 for this container (shown in FIGS. 9 and 10) fitsaround the perimeter 80 and may be designed with (FIG. 9) or withoutapertures (FIG. 10).

In FIG. 11, cap 51 is shown with elongated apertures 73 which can beopened or closed by closure means, not shown, and which can be fittedover perimeter 80.

In an alternative embodiment, FIG. 12 shows a container 100 having agenerally elongated tubular shape defined by wall 110 and having adispense end 112 defined by a fiber tip dispenser 114. Cap 116 as shownis designed for closingly engaging tubular wall 110 by a pressure fitengagement with flange 118. Desirably, cap 116 engages the tubular wall110 at flange 118 to provide a barrier against ambient humidity toprevent premature curing of the cyanacrylate adhesive compositiondisposed with container 110. FIG. 13 shows composition 120, within acollapsible interior liner 122, being advanced to the fiber tipdispenser using knurled knob 124 which is turned to mechanically advancethe composition within the container 110.

In an alternative embodiment FIG. 14 shows container 100 having agenerally elongated tubular shape defined by wall 110 and having adispense end 126 defined by solid end 128 with circular apertures 130.

In an alternative embodiment FIG. 15 shows container 100 having agenerally elongated tubular shape defined by wall 110 and having adispense end 132 defined by a dispenser 134.

In an alternative embodiment FIG. 16 shows container 100 having agenerally elongated tubular shape defined by wall 110 and having adispense end 136 defined by a vertical oriented roller 138.

In an alternative embodiment FIG. 17 shows container 100 having agenerally elongated tubular shape defined by wall 110 having a dispenseend 140 defined by a horizontally oriented roller 142.

In a further alternative embodiment, FIGS. 18-20 show a dispenser 200having a generally cylindrical container 202 and having a dispensing end204 defined by an actuator 206 for dispensing a flowable liquid. Thecontainer 202 has a generally elongated tubular shaped body 208,consisting of a lower body portion 210 and an upper body portion 212.The lower body portion is defined by a generally cylindrical wall 214, abottom plate 216 and a top wall 218 defining a lower body cavity 220 forcontaining, under pressure, a flowable liquid 222. The upper bodyportion 212 consists of a generally cylindrical upwardly depending openwall portion 224 defining an upper body cavity 226.

The actuator 206 consists of an actuator body 228 and dispensing head230 with an aperture 232 for releasing liquid upon activation of thedispense head. The actuator body 228 has an open upper portion 234 forreceiving the dispensing head 232 in fixed relation thereto and adownwardly depending open lower portion 236 defined by a lower portiongenerally cylindrical wall 238 and a top wall 240 defining an actuatorbody lower portion cavity 242. The actuator body lower portion 236 isslideably received in the upper body portion 212 and retained therein byan upper lip 244 on the upper body portion.

The lower body portion top wall 218 has a valve receiving opening 246for slideably receiving therein a lower valve 248. The actuator bodylower portion top wall 240 has a valve receiving opening 250 forslideably receiving therein an upper valve 252. A bellows assembly 254is disposed between the actuator body lower portion top wall and lowerbody portion top wall 218,240 to retain flowable liquid in a pressurizedcondition.

The lower body portion cavity 220 retains a piston 256 in slidingrelation to maintain the flowable liquid 222 in a pressurized conditionin cavity 220.

Cap 258 as shown is designed for closingly engaging the container upperbody cylindrical wall portion 224.

The lower valve opening 246 consists of a valve seat 251 for sealinglyengaging a lower valve member 253 on lower valve 248. Lower body portiontop wall 218 also has four (only two shown) valve retaining members 255for limiting the upper movement of lower valve 248.

The upper valve opening 250 consists of a valve seat 257 for sealinglyengaging an upper valve member 259 on upper valve 252.

In a further embodiment, FIGS. 21-24 show a dispenser 300 having asubstantially cylindrical body unit 310. The body until 310 includes anexterior cylindrical fluid reservoir 312 and an interior cylindricalfluid reservoir 314. Both reservoirs 312, 314 comprise the entire lengthof the body until 310. The exterior cylindrical fluid reservoir 312includes an exterior circular base plate 316 defining a lower wall ofthe exterior cylindrical fluid reservoir 312. The interior fluidreservoir 314 includes an interior circular base plate 318 defining thelower wall of the interior cylindrical fluid reservoir 314. The bodyunit includes a circular base plate 320 that defines the bottom portionof the body unit 310. The base plate 320 further includes a circularopening 322 for receiving the interior circular base plate 318.

The external cylindrical fluid reservoir 312 has an external fluidopening 324 in the upper wall portion 326 of the external cylindricalfluid reservoir 312. Likewise, the internal cylindrical fluid reservoir314 has an internal fluid opening 328 in the upper wall portion 330 ofthe internal cylindrical fluid reservoir 314. Additionally, there is adetent 332 and corresponding alignment pin 334 to aid in properalignment of a valve assembly until 326.

The valve assembly unit 336 is pressure mounted atop the body unit 310.The valve assembly unit 336 includes an interior dip tube 338, which issubstantially similar in size to the internal fluid opening 328. Thevalve assembly unit 336 also includes an exterior dip tube 340, which issubstantially similar in size to the internal fluid opening 324. Thefluid openings and corresponding dip tubes each have a differentdiameter to ensure that there is only one correct orientation of thevalve assembly unit 336 with the body unit 310.

The valve assembly unit 336 has an interior valve seat 342, with aninterior check ball 346 on the valve seat 342. Additionally, the valveassembly 336 also comprises an exterior valve seat 348, with an exteriorcheck ball 350 on the exterior valve seat 348. The valve assembly unit336 includes an exterior cylindrical retaining wall 352 and an interiorcylindrical retaining wall 354 which includes a plurality of retainingtabs 356.

A mixing unit 358 is pressure fit within the interior retaining wall354. The mixing unit 358 includes an interior dip tube 360, whichconnects to the valve assembly unit 336, and creates a first mixingchamber 362. The mixing unit 358 also includes an exterior dip tube 364that connects to the valve assembly unit 336 and forms a second mixingchamber 366. The mixing unit 358 includes a mixing unit exteriorretaining wall 368 which along with the interior retaining wall 354forms the lower portion of a spring housing cavity 370 which housesspring 376. The mixing unit and interior dip tube 360 has a slitcreating a passage 374 connecting the second mixing chamber 366 with thefirst mixing chamber 362.

An actuator body unit 378 is substantially cylindrical and is pressuremounted to the mixing unit 358. The actuator body unit 378 is secured tothe mixing unit 358 by multiple retaining tabs 380 that interlock withthe valve assembly unit retaining tabs 356. The actuator body unit 378has an exterior actuator retaining wall 382, which fits within themixing unit exterior retaining wall 368. The actuator body unit definesthe upper wall section of the second mixing chamber 366. The actuatorbody unit 378 also has an actuator interior dip tube 384, which iscylindrical in shape, and includes a valve seat 386 and a check ball388. The actuator body unit 378 has a gasket 390 and a cylindrical upperretaining wall 392 that creates a reservoir. The cylindrical upperretaining wall 392 has a portion removed from the circumference creatinga passage way for an upper outlet channel 394.

A substantially cylindrical dispensing head 396 is pressure mounted tothe actuator body unit 378. The dispensing head 396 has a substantiallycylindrical exterior retaining wall 398, which fits within thecylindrical upper retaining wall 392. The dispensing head has a loweroutlet channel 400 that is connected to the upper outlet channel 394 anddispensing head aperture 402. Additionally there is a substantiallycylindrical cap 404 that is pressure mounted to the body unit 310, andsurrounds the dispensing head and is mounts to a cap ridge 406.

In an alternative embodiment, FIG. 25 shows a dispenser 500 having asubstantially cylindrical body unit 510. The body unit is 510 is dividedinto a first hemicylinder fluid reservoir 512 and a second hemicylinderfluid reservoir 514. An upper wall 516 of the body unit has a firstcircular opening 518 and a second circular opening 520. The upper wallof the body unit 510 further includes two retaining slots (not shown)for receiving retaining tabs (not shown).

A valve assembly unit 522 is mounted to the body unit 510 and secured bythe interlocking of the tabs (not shown) and slots (not shown). Thevalve assembly unit 522 also includes a first actuator housing 524having a first cylindrical opening 524 and a second actuator housing 528having a second cylindrical opening 530. A first modular casing 532 ispressure fit into the first actuator housing 524. A second modularcasing 532 further includes a first interior plunger 536, having a firstplunger head 538 and first plunger shaft 540. The first plunger head 538further includes a first gasket 542 for proving a watertight sealbetween the first interior plunger 536 and a first exterior retainingwall 544. Additionally, there is a first interior O-ring 546 forproviding a watertight seal at the base of the first exterior retainingwall 544. The first exterior retaining wall 544 is pressure fit withinthe first modular casing 532 and further includes an exterior O-ring 548for providing a watertight seal between the first exterior retainingwall 544 and the first modular casing 532.

Similarly, the second modular casing 534 further includes a secondinterior plunger 550, having a second plunger head 552 and a secondplunger shaft 554. The second plunger head 552 further includes a secondgasket 556 for proving a watertight seal between the second interiorplunger 550 and a second exterior retaining wall 558. Additionally,there is a second interior O-ring 560 for providing a watertight seal atthe base of the second exterior retaining wall 558. The exteriorretaining wall 558 is pressure fit within the second modular casing 534and further includes an exterior O-ring 562 for providing a watertightseal between the second exterior retaining wall 558 and the secondmodular casing 534.

The modular casings 532, 534 define an upper wall portion 516 of thefluid reservoirs 512, 514 respectively. The plunger heads 538, 552define an upper wall portion for fluid chambers 564 and 566respectively. The interior plungers 536, 550 also have small openingsand are hollow to provide a first pathway 568 and a second pathway 570connecting the fluid chambers 564 and 566 to the dispensing head 572.Additionally, the first modular casing 532 has a second exterior O-ring576.

Coiled around the actuator housing units 524, 528 are first spring 578and second spring 580.

Additionally, and as shown in FIG. 28, there is a substantiallycylindrical cap 582 that is pressure mounted to the body unit 510 whichsurrounds the dispensing head 572 and mounts to a cap ridge 584.

Referring to FIG. 29, the dispensing head 572 has a first down tube 586that receives the first pathway 568, thus defusing a first lower outletchannel 588. The first lower outlet channel 588 connects to a firstupper outlet channel 590, and arcs toward a first aperture 592.

Likewise, the dispensing head 572 has a second down tube 594 thatreceives the second pathway 570, thus defining a second lower outletchannel 596. The second lower outlet channel 596 connects to a secondupper outlet channel 598, and arcs toward a second aperture 600. Theapertures 592, 600 are positioned next to each other such that thefluids are dispensed from separate reservoirs, but are still dispensedsimultaneously to the user.

Referring to FIG. 30, in another embodiment, the first and second upperoutlet channels 590, 598 respectively could be combined into a singleaperture 602. This would function similarly to the previous embodiment,except that the fluids would be combined in the upper outlet channels590, 598 just prior to exiting the dispensing head 572 through thesingle aperture 602.

Other useful dispensers or applicators are disclosed in InternationalPatent Publication No. WO 01/91915, the contents of which areincorporated herein by reference. The applicators include a seal formedbetween the dispenser opening and its mating cap to prevent prematurepolymerization of cyanoacrylate adhesive compositions without thedispenser or container body.

The following non-limiting examples are intended to further illustratethe present invention.

EXAMPLES Example 1

Cyanoacrylate compositions A and B were prepared by incorporating theindicated amount of polymeric material in powder form and thickener andmixing in a dispenser for about 30 seconds, though 5 minutes or longermay be desirable, until the polymeric powder is dispersed in thecyanoacrylate composition. The cyanoacrylate composition may optionallybe slightly heated prior to incorporation of the polymeric material,e.g., at about 122° F. (50° C.).

TABLE I INVENTIVE NON-FLOWABLE CYANOACRYLATE COMPOSITIONS CompositionComponent (wt. %) Type Identity A B CA Ethyl cyanoacrylate monomer 75 75Thickener Polymethylmethacrylate  7  7 Polymeric Materialtrihydroxystearin⁽¹⁾ 15 — Polymeric Material hydroxylated caster oil —15 derivative⁽²⁾ Iinhibitor BF₃, ppm 18 18 ⁽¹⁾THIXIN R ⁽²⁾THIXIN E

Each of the inventive compositions were dispensed into lipstick-typealuminum dispenser packages and postbaked at about 122° F. (50° C.) oraged overnight at that temperature. In the present invention, thesematerials allow for a normally room temperature flowable composition,such as a cyanoacrylate composition, to be rendered non-flowable at roomtemperature and remain non-flowable up to temperatures of 180° F. (82°C.) or more. In each of the inventive compositions 1-5, the resultantcomposition, even after accelerated heat aging, was a self-supportingadhesive mass, exhibiting a soft non-flowable consistency which waseasily dispensed onto substrates by wiping the dispenser across theintended surface.

Lap shear specimens were prepared for these compositions using standardsteel substrates each having the same amount of composition placed ontothe substrate. The inventive non-flowable compositions were applied bymanual application from a lipstick-type dispenser. The prepared sampleswere cured at temperatures given below. The specimens were pulled at 0.5inches/minute per ASTM D1002. The inventive compositions were comparedto a control, i.e., a flowable cyanoacrylate composition. The lap shearstrengths in psi were recorded, as follows in Table II.

TABLE II Lap Shear Strength Tests (psi) Compositions Curing ConditionsLap Shear Strength (psi) Inventive Room temperature, 2,800 Composition A24 hours Inventive Room temperature, 3,000 Composition B 24 hoursControl-A (liquid Room temperature, 3,400 cyanoacrylate)⁽¹⁾ 24 hoursControl-B (gel Room temperature, 3,400 cyanoacrylate)⁽²⁾ 24 hoursControl-C (gel Room temperature, 3,200 cyanoacrylate)⁽³⁾ 24 hours ⁽¹⁾Aliquid in the uncured state having a 15 to 25 mPas (cP)Viscosity,Brookfield - LVF, 25° C., Spindle #1, Speed 30 rpm. Commerciallyavailable as LOCTITE ® 406. ⁽²⁾A gel in the uncured state having a15,000 to 40,000 mPas (cP) Viscosity, Brookfield - RVF, 25° C., Spindle#TC, Speed 20 rpm, Helipath. Commercially available as LOCTITE ® 409.⁽³⁾A gel in the uncured state having a 18,000 to 40,000 mPas (cP)Viscosity, Brookfield - RVT, 25° C., Spindle #TC, Speed 20 rpm,Helipath. Commercially available as LOCTITE ® 454.

The inventive compositions had lap shear strengths comparable tocommercially available liquid and gel cyanoacrylate products.

The inventive compositions were stable when stored in containers, suchas aluminum tubes. Accelerated stability tests were done at 82° C., asfollows:

TABLE III Accelerated Stability Tests Compositions Storage ConditionsStability⁽⁴⁾ (days) Inventive 82° C., aluminum >14 Composition A tubesInventive 82° C., aluminum >14 Composition B tubes Control-A (liquid 82°C., aluminum >14 cyanoacrylate)⁽¹⁾ tubes Control-B (gel 82° C.,aluminum >14 cyanoacrylate)⁽²⁾ tubes Control-C (gel 82° C., aluminum >14cyanoacrylate)⁽³⁾ tubes ⁽¹⁾A liquid in the uncured state having a 15 to25 mPas (cP)Viscosity, Brookfield - LVF, 25° C., Spindle #1, Speed 30rpm. Commercially available as LOCTITE ® 406. ⁽²⁾A gel in the uncuredstate having a 15,000 to 40,000 mPas (cP) Viscosity, Brookfield - RVF,25° C., Spindle #TC, Speed 20 rpm, Helipath. Commercially available asLOCTITE ® 409. ⁽³⁾A gel in the uncured state having a 18,000 to 40,000mPas (cP) Viscosity, Brookfield - RVT, 25° C., Spindle #TC, Speed 20rpm, Helipath. Commercially available as LOCTITE ® 454. ⁽⁴⁾Equivalent toabout two years and greater shelf life at room temperature.

The inventive compositions had shelf lives comparable to commerciallyavailable liquid and gel cyanoacrylate products.

What is claimed is:
 1. An article of manufacture comprising: a. adispensing container for housing and dispensing a non-flowable adhesivecomposition, said container comprising a generally elongate hollow bodyhaving first and second ends, with one of said ends defining a dispenseopening; and b. a cyanoacrylate composition within said container, saidcomposition comprising: (i) at least one cyanoacrylate monomer; and (ii)a polymeric matrix selected from the group consisting ofhydroxy-modified aliphatic hydrocarbons, polyester-based rheologicaladditives and combinations thereof, present in an amount sufficient torender said compositions non-flowable at temperatures up to about 180°F.
 2. The article of claim 1, further comprising a brush at the dispenseopening.
 3. The article of claim 1, further comprising a pad at thedispense opening.